Production of ammonia.



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FFEQQ FREDEIK W. m; JAHN, 01? NEW YORK, N. Y., ASSIGNOR TO GENERAL CHEMICAL COMPANY, OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

, PRODUCTION OF AMMONIA.

Ne Drawing.

T aZZ W llem tin/1y com-em lle it known that .l, l uumuz; W. on JAIIN, a subject of the Kirg of Norway, and a resident of the borough oi Manhattan, city, county, and State of New York, have invented certain new and useful Improvements in the Production of Ammonia, of which the following is a specification.

lily invention relates to the synthetic production of ammonia and more particularly to a new catalytic agent therefor, its production and use.

l: have discovered. that if a gaseous mixture containing nitrogen and hydrogen is suitably passed in contact with a suitable material composed essentially of (1) nitrogen, (2) an alkali metal such as sodium or potassium,and (3) one or more of the fol lowing metals, all of which are for the purpose of this invention equivalentsz manganese, cobalt, cerium, boron, titanium, uranium, and silicon, the nitrogen and hydrogen oi the gaseous mixture are united to form ammonia.

in order that my invention may be clearly uiulerstood, itis now set forth. in the form of specific examples, it beingunderstood, of course, that the invention is not to be limited to the exact materials or proportions thereof nor to the temperatures or other conditions of the exzm'iplcs, since these may be varied without departing from my invention.

it is also to be umlerstood that a catalyzer may contain either manganese, cobalt, cerium, boron, titanium. uranium, or silicon, together with an alkali metal and nitrogen,

or may contain. two or more of these metals I together with an alkali metal and nitrogen; in the latter case the percentage oi the alkali metal plus nitgrogen in the catalyzer is prei erably not varied, that is to say, for example, it instead of cobalt in the catalyze! it is desired to substitute :obalt and titanium, tho propm'tion oi the cobalt and titanium combined, to the alkali metal and nitrogen combimahis sul'istantially the same as the pro portion of cobalt to the alkali metal and nitrogen combined, in the original catalyzer, while the ratio of the cobalt to the titanium may be any ratio desired. in a like manner,

part or all of the particular alkali metal mentioned, say" sodium, may be replaced by another alkali metal, as "for instance, po-

Specification of Letters Patent.

Patented June 8, 1915.

tassium. Moreover the manganese, cobalt, cerium, boron, titanium, uranium, and silicon, whether said metals are used in the catalyzer singly or in associated relation, may be replaced in part by iron, nickel, and molybdenum, which last mentioned metals are more specifically referred to and claimed in. my pending application, Serial No. 782,096, filed August 2, 1913, the present invention being in the nature of an improvement over the invention of said pending application.

[imam 1Z0 1-Prcparing the catalytic mazcriaZ.Pi.unicc stone in small pieces is pnri fied by treatment with hydrochloric acid for about twenty-four (24;) hours; it is then' washed with distilled wateruntil free from chlorid and then ignited to dryness.

A. Of this product 100 grams are treated with substantially the atomic Weight in grains (5!) grams) of cobalt in the form of nitrate dissolved in the necessary quantity of water, say 150 grams of water, and the whole is evaporated to dryness, being stirred thoroughly during the evaporation; in this way the cobalt is to be uniformly distributed over the pumice. The thus treated pumice is now ignited at about 550 C. until fumes are no longer given oil and is then heated at about the same temperature in an atmosphere of hydrogen until Water is no longer formed. To this product, when cooled in an indi tlj'erent atmosphere such as hy-lrogen and while still in such atmosphere, add (39 grams of metallic sodium (or 117 grams of metallic potassium) in small pieces and then heat the whole l'orlhe purpmec of melt ng the sodium and distribute the molten sodium over the surface ol the pumice ur" rzal as. for example, bysuitable contii .il stirring; dis place the indifferent gas by anhydrous ammonia vapor or gas and heat the material to about 300 while passing ammonia vapor until a przuztically constant weight is=obtaiuedQ. Preserve the material, after being cooled, ready for use in, for example, a dry atmosphere of ammonia.

of cobalt in the form of nitrate in the foregoing example A, I can use the atomic 10o B. In place of-the atomic weight in grams Weight in grams of manganese, or titanium,

preferably in the term of chlorid.

O. In place of the hydrogen need in treat- 2. Lie-1,8418

' ingthe ignited pumice and cobaltor the like material, I can use a mixture .of nitrogen and hydrogen or other suitable reducing gas. D. In the ease of the elements cerium, uranium and silicon, I have foundiit adyan- .agcous to treat the prepared pumice with the chlorids of these elements in the same manner as with the nitrate of cobalt of the preceding and toeffect the formation of a .suitable product by the use of metallic so- Qdium (in place of hydrogen) and heat;

sodium I may use the equivalent amount of.

metallic potassium). Heat the result of such treatment to about 300 C. until the further formation of sodium chlorid substantially ceases: then treat with hot distilled water until practically all the watersoluble chlorid has'been removed; now wash well with distilled water and dry by gentle heating in an indifferent atmosphere such as hydrogen; now add H1 each ca se 69 grams of metallic sodium or the equivalent amount of metallic potassium: heat to a temperature just above the melting; point of thesodium and distribute the molten sodium uniformly over the surface of the pumice material, as, for example, by suitable'continuedstirring. Now displace the hydrogenor other indiffere'nt gas by means of anhydrous ammonia vapor or gas and raise the temperature of the whole to 300 C. and maintain that condition until a practically constant Weight is obtained; after cooling preserve the material ready for use in. a dry atmosphere of, for example, ammoni E. In the case of boron, I prefer to 'proce'ed as follows: make a paste of the ele ment in finely powdered condition (for 'eX- ample, in the so-called impalpable powder form) with water and thoroughly com:

mingle this paste with the aforementioned prepared pumice While applying heat in sufficient and proper amount and rate'to drive off substantially all of the water: add to the result a quantity of metallic sodium amounting to 6D Jramsof'mctallic sodium for each atomic weight in grams of the boron. Which has been ascertained to have been aflixed'to the preparcdpumice in each case. Take the (3.) grams of. metallic sodium or their prop rtionate bright determined as above, in

inely divided condition, and heat tlieiwhble in all-indifferent atmosphere s'i'i'cha's hydrogen to just above the melting point of the sodium and distribute the molten sodium uniformly overthe surface of thepumice ring. Now displace the hydrogen orother indifferent gas by means of anhydrous ammonia vapor or as and raise the, tempegeture of'the whole to 300 C. and maintain in that condition until a practically constantmaterial, as, for example, by contiiiu'ed stir 71 weight is obtained; after cooling preserve the material ready for use in, for example, a dry atmosphere of ammonia. v

F. It is also useful to prepare catalysts containing more than one of the above named non-alkali elements. For instance, in example A, I can use in place of the 59 grams of the element cobalt, 29.5 grams thereof and 24 grams of the element titanium, both in the form of chlorid. can use the (39 gramsof sodium ora portion thereof putting in the place of the omitted portion an equivalent amount of metallic potassium, or I may, put in place of the 69 grams of metallic sodium 117 grams ofmetallic potassium. In example A I can also use in place of the 59 grams of the element cobalt 16 grams each of the elements iron, cobalt and titanium, all in the form of chlorid. I can also suitably use combinations of the elements iron. nickel, and cobalt as mixed nitrates and chloride as circumstances ma y indicate or make desirable. The methods used in I) or E above can also be applied to all the other elements if desired,

but .I prefer the inethcds'above giyen for the respective elemcnts recited. Sodium or potassium amid canbe used and the pumice or other suitable carrier maybe omitted. By these methods or a suitable combination of all or part 'of them. it is possible to produceany desired combination of elements as catalysts. n

Example lll7tz'li zz'ng the catalytic to produce amm-onia.-For producing ammonia about 175'grams of the product of example A, above, or acorresponding' amount 'of its equivalent, are placed in a suitable catalytic chamber for ammonia synthesis and there passed in contact with such :eatalyzer a gas current preferably contain ing one volume of nitrogen for every three volumes of hydrogen. The gas mixture .must be suitably purified and must be freed especially from contact poisons in the Well knownmanner. With the'pressure of the gas traversing the chamber. Within the. range'of 80 to 90 atmospheres and the tem perature of treatment approximately between 520 C. and 540 (1, I have succeeded in producing synthetic ammonia to the extent that the ammonia gas leaving the treating chamber constituted 416.5% by volume of mamas the total gas leaving such chamber. The

charged from thecatalytic chamber in any suitable manner.

Wherever in this specification min the claims annexed thereto I have used the Word cobalt, I mean of course to include therein each and all of the aforementioned equivalents thereof, either alone or in mixture with each other; likewise when in this specification or in the claims thereto annexed I have used the Word sodium, I mean to include in that term the equivalent thereof disclosed herein, namely, potassium. Moreover, when in theclaims I specify broadly or specifically in the making of the catalyzer that (A) cobalt (or its equivalent) is added to (B) an alkali metal, and the pr'oductfthus formed is treated with (O) a gas containing nitrogen, I mean to include also the equivalents of such process, among which equivalents I mention theaddition of '(A) cobalt to the product resulting from the treatment of the metal (B) with the gas (0) ;'-the addition of the metal (B) to an oxid or suitable salt of the metal (A) fol lowed by the reduction of the compound of the metal (A) as by hydrogen, the resulting product being then treated With the gas (0) and the addition of a suitable compound,

such as an amid, of the metal (B) to the metal (A).

I claim:

1. The herein described process of producing ammonia, which comprises suitably passing a gaseous mixture containing nitrogen and hydrogen in contact with a-heated 2. The herein described process of pro+ 3. The herein described process of pro-' ducing ammonia, Which comprises suitably passing a gaseous mixture containing nitrogen and hydrogen under a pressure less than 100' atmospheres in contact with a heated catalytic agent containing (1) cobalt, (2)

sodium and (8) nitrogen. 40 I ducing ammonia, which comprises suitably catalytic agent containing (1) cobalt, (2) I .sodium'an'd- :(3) nitrogen.

In testimony whereof I have hereunto set .my hand in the presence of two subscribing withessesi i v FREDRI K W. as JAHN.

Witnesses: I

FRITZ ZmGLEmJL,

R. ABE-ELY. 

